Two-phase acidic aqueous compositions for diffusion transfer products

ABSTRACT

A two-phase acidic aqueous composition for use as a neutralization layer is generally comprised of a water soluble aqueous phase and a water insoluble particle phase. The particle phase generally comprises a copolymer having recurring units of an organic acid monomer and an organic ester monomer. The aqueous phase comprises a water soluble polymer having recurring units of at least an organic acid monomer. The organic acid monomers selected for the aqueous phase polymer are capable of interacting with the particle phase polymers such that the particle phase polymers are brought into stabilizing, intimate association with the aqueous phase.

This application is a division of application Ser. No. 08/189,105, filedJan. 31, 1994 now U.S. Pat. No. 5,427,899.

FIELD OF THE INVENTION

The invention generally relates to a two-phase acidic aqueous polymericsystem with a high-acid particle phase, and more particularly, to atwo-phase acidic aqueous polymeric acid neutralizing system with ahigh-acid particle phase, the neutralizing system having acidneutralization capabilities and being suitable for incorporation intodiffusion transfer products and processes.

BACKGROUND OF THE INVENTION AND DESCRIPTION OF THE PRIOR ART

Diffusion transfer products and processes have been the subject ofseveral patents, including for example, U.S. Pat. Nos. 2,983,606;3,345,163; 3,362,819; 3,594,164; and 3,594,165.

In general, diffusion transfer photographic products and processesinvolve film units having a photosensitive system including at least onesilver halide layer, usually integrated with an image-providingmaterial, e.g., an image dye-providing material. After photoexposure,the photosensitive system is developed, generally by uniformlydistributing an aqueous alkaline processing composition over thephotoexposed element, to establish a diffusible imagewise distributionof the image-providing material. The image-providing material isselectively transferred, at least in part, by diffusion to animage-receiving layer or element positioned in a superposed relationshipwith the developed photosensitive element, the image-receiving layerbeing capable of mordanting or otherwise fixing the image-providingmaterial. The image-receiving layer retains the transferred image forviewing, and in some diffusion transfer products, the image is viewed inthe image-receiving layer after separation from the photosensitiveelement (e.g., "peel apart" film units), while in other products, suchseparation is not required (e.g., "integral" film units).

Image-dye providing materials which may be employed in diffusiontransfer processes generally may be characterized as initially solubleor diffusible in the processing composition but selectively renderednondiffusible in an imagewise pattern as a function of development, oras initially insoluble or nondiffusible in the processing compositionbut selectively rendered diffusible in an imagewise pattern as afunction of development. These materials may contain complete dyes ordye intermediates, e.g., color couplers. A particularly useful class ofimage-dye providing materials for diffusion transfer processes are dyedevelopers. These compounds contain, in the same molecule, both thechromophoric system of a dye and also a group adapted to develop exposedphotographic silver halide.

Although the principles and subject matter presented herein are readilyadaptable to other diffusion transfer products and processes, in orderto facilitate the presentation herein, representative diffusion transferproducts and processes utilizing dye developer image-dye providingmaterials have been selected to be discussed in more specific detailbelow.

Multicolor images in a representative diffusion transfer system can beobtained by arranging a photosensitive element with at least two silverhalide layers selectively sensitized to different regions of thespectrum. Such a system is shown, for example, in U.S. Pat. No.2,983,606. To accomplish subtractive color photography, associated witheach silver halide layer is a dye developer featuring an absorption thatis substantially complementary in color to the color of the lightrecorded in the contiguous silver halide layer. The most commonlyemployed arrangement of this type includes three monochrome units--ablue-sensitive silver halide layer overlying a yellow dye developer, agreen-sensitive silver halide layer overlying a magenta dye developer,and a red-sensitive silver halide layer overlying a cyan dye developer.

Such an exposed photosensitive dement is processed using an aqueousalkaline processing composition containing an alkali, such as potassiumhydroxide. The processing composition penetrates the layers of thenegative element and dissolves the dye developer compounds by ionizingthe developer groups. In each silver halide layer, where the silverhalide has been exposed and developed, the dye developer becomesinsoluble or at least substantially immobile. In unexposed regions ofsilver halide, the solubilized dye developer diffuses through theoverlying layers to an image-receiving layer to form a positivemulticolor image.

The photographic transfer dye image frequently retains substantialamounts of photographic reagent, particularly alkali, with which it hasbeen processed, even though the layer of processing composition iscaused to adhere to and remain with the photosensitive layer. Thepresence of those residual reagents may adversely effect the quality andstability of the image, particularly in the presence of significantquantities of alkali. For example, if the receiving layer is highlyalkaline, oxidation by atmospheric oxygen of unreacted developing agentor other component of the processing composition is quite likely tooccur, and such reactions or subsequent reactions may impart a stain orotherwise discolor the transfer image, particularly the highlightsthereof.

Since the processing compositions employed in diffusion transferproducts and processes are highly alkaline (i.e., pH>12), afterprocessing has been allowed to proceed for a predetermined period oftime, it is desirable to treat the image-receiving element with asolution which is effective to remove (as by a washing action),neutralize or otherwise render such processing agents relativelyinnocuous. A neutralizing layer, typically a nondiffusible polymericacid-reacting agent, has been employed in previous diffusion transferfilm units to lower the pH from a first (high) pH of the processingcomposition to a predetermined second (lower) pH. See e.g., U.S. Pat.No. 3,362,819, issued to E. H. Land on Jan. 9, 1968. In this regard, thepolymeric acid, acting as an ion exchanger, forms an immobile polymericsalt with the alkali cation and returns water in place of alkali.Capture of alkali by the polymer molecule prevents deposition of saltson the print surface. The dye developers thus become immobile andinactive as the pH of the system is reduced. As examples of otherpreviously :patented neutralizing layers, in addition to those disclosedin the aforementioned U.S. Pat. No. 3,362,819, mention may be made ofthose disclosed in the following U.S. patents: Bedell U.S. Pat. No.3,765,885; Sahatjian et at. U.S. Pat. No. 3,819,371; Haas U.S. Pat. No.3,833,367; Taylor U.S. Pat. No. 3,756,815 and Schlein U.S. Pat. No.3,756,815.

In Land '819, as with most other previous systems, the polymeric acidneutralization layer was typically deposited onto a dimensionally stablesubstrate by means of an organic solvent, such as acetone, methyl ethylketone, methanol, ethyl acetate, butyl acetate, and mixtures thereof.While organic solvent-based neutralization layers continue to be used,interest has expanded toward the development of an aqueous-based (i.e.,water soluble) neutralization layer.

The use of water-soluble ingredients in the neutralizing layer affordsseveral distinct advantages over systems employing water-insolublesolvent-coated components. Apart from the readily apparent advantage inavoiding the use of organic solvents, water-soluble compositions mayutilize shorter acid molecules with lower equivalent weights, therebypermitting one to employ thinner coatings. Advantage is gained, sincethe neutralization layer, in certain diffusion transfer products, shouldbe as thin and clear as possible in order to minimize distortion and/orto obtain the most optimal resolution.

Despite advantage, previous efforts to provide aqueous-basedneutralization layers, resulted almost invariably in film units with anunacceptable and unresolvable propensity to curl. See, Schlein '815.Curling was most evident prior to use, making subsequent processing ofthe film unit for image formation difficult. Curling also manifested inthe finished print, which was and continues to be undesirable from anaesthetic standpoint. To the extent that it occurred, gains in thecontrol of cud in aqueous-based systems of previous efforts came at thesacrifice of other aspects of sensitometric performance and/or theunacceptable increase of manufacturing costs.

In view of the above, there has been a long-felt and yetunsatisfactorily resolved need for a composition useful in making acurl-resistant aqueous-based neutralization system having desirable,functional characteristics, such as adequate acid neutralizationcapabilities, thinness, and clarity. Related need also exists for viableand effective methods for making the compositions used for suchneutralization layers.

SUMMARY OF THE INVENTION

Responsive to the aforementioned need for an aqueous neutralizing layer,the present invention provides a two-phase acidic aqueous composition.The two-phase acidic aqueous composition generally comprises a watersoluble aqueous phase and a water insoluble particle phase. The particlephase generally comprises a copolymer having recurring units of anorganic acid monomer (in a principal embodiment, e.g., acrylic acid) andan organic ester monomer (in a principal embodiment, e.g., butylacrylate). The aqueous phase comprises a water soluble polymer havingrecurring units of at least an organic acid monomer. The organic acidmonomers selected for the aqueous phase polymer are capable ofinteracting with the particle phase polymers such that the particlephase polymers are brought into stabilizing, intimate association withthe aqueous phase. Properly configured in accordance with the presentinvention, the composition remains stable with age, and when used in aneutralization layer for diffusion transfer products, promotesheightened resistance to curl.

Several and diverse applications of the composition are envisioned. Useas a neutralization layer for diffusion transfer products is theprincipal application of the composition. For such products, methodaspects of the present invention described herein seek to align thedemands of industrial manufacture together with the need to obtain aproduct with rheological and sensitometric properties most appropriateto its desired end-use. As to the demands of manufacture, chief concernsof design included the reduction of microaggregate and coagulumformation and the reduction of avoidable manufacturing costs.

According to method aspects of the present invention, there is disclosedand described methods of synthesizing the two-phase high-acid aqueouscomposition of the present invention, the several embodiments of whichgenerally subsist in variations of a polymerization process involving aninitial colloidal stabilization step. In one embodiment, colloidallystabilized preparation of a particle phase is followed by "blending"with components of a desired aqueous phase. In another embodiment, thecolloidal stabilizer is prepared in situ, followed by a simultaneouspolymeric synthesis of both aqueous and particle phases. In a thirdembodiment, the colloidal stabilizer is again prepared "in situ", butfollowed by a "step-wise" polymeric synthesis of both aqueous andparticle phases.

In light of the above, it is a principal object of the presentinvention, to provide an acidic aqueous composition that may beincorporated into a diffusion transfer product as a neutralization layerwithout effecting an undesirable degree of curl.

It is another object of the present invention to provide a stabletwo-phase acidic aqueous composition having a particle phase and aqueousphase, wherein the particle phase has a comparatively high acid content.

It is another object of the present invention to provide a method forthe synthesis of stable two-phase acidic aqueous compositions, themethod capable of achieving an effectively reduced formation ofmicroaggregates.

It is another object of the present invention to provide a method forthe synthesis of stable two-phase acidic aqueous compositions, themethod not requiring use of commercially available polymeric acids.

It is another object of the present invention to provide a comparativelylow-cost single reactor method for the synthesis of stable two-phaseacidic aqueous compositions, the method capable of achieving aneffectively reduced formation of microaggregates.

It is another object of the present invention to provide a comparativelylow-cost single-reactor method for the synthesis of stable two-phaseacidic aqueous compositions, the method capable of achieving aneffectively reduced formation of both microaggregates and coagulum.

For a fuller understanding of the nature and objects of the presentinvention, reference should be had to the following detailed descriptiontaken in connection with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of an image-receiving elementof an embodiment of a photographic application of the inventioncomprising a support material; a neutralization system according to thepresent invention, a timing layer, an image-receiving layer and anovercoat layer.

FIGS. 2 to 4 are schematic cross-sectional views of particulararrangements of film units, shown after exposure and processing, eachhaving a neutralization layer into which the composition of the presentinvention may be incorporated.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a two-phase acidic aqueous compositionthat remains stable with age, and when incorporated into, for example,diffusion transfer products, effects good curl performance. Thetwo-phase acidic aqueous composition generally comprises a water solublephase and a water insoluble particle phase. The particle phase generallycomprises a copolymer having recurring units of an organic acid monomerand an organic ester monomer.

The particle phase is comparatively highly acidic (cf., "high-acidparticle phase"), a condition effected by the comparatively highconcentrations of acidic monomers that recur in the particle phasepolymer. The concentration of the organic acid monomer utilized for theparticle phase polymer of a preferred composition will approximate20%-30% of the polymer (by weight), with an acceptable range,appropriate for some purposes, as broad as approximately 10% toapproximately 40%. The remainder of the particle phase polymer comprisesorganic ester monomer units. The organic ester monomer componentsprovide the particle phase with "softness", low modulus, low Tg, andpromote the insolubility of the particle phase in the aqueous phase.Such functionality is considered in the selection of appropriate organicester monomers, or equivalents.

The aqueous phase comprises a water soluble polymer having recurringunits of at least an organic acid monomer. In certain embodiments, theaqueous phase polymer will be a homopolymer of an organic acid monomer,in other embodiments, it will be a copolymer of an organic acid monomerand an organic ester monomer. Where the aqueous phase is a copolymer,the ratio of the organic acid monomer to the organic ester monomershould be such that the organic acid monomer dominates to a degreewherein the copolymer is operatively water soluble. In a preferredcomposition, the organic monomer selected for aqueous phase polymer willbe the same as the organic ester monomer selected for the particle phasepolymer. For embodiments where the aqueous phase is a homopolymer,commercially available linear organic polymeric acids may be utilized.

The organic acid monomers that may be considered for use, alone or incombination, for either the particle phase of the aqueous phase of thepresent invention include ethylenically unsaturated carboxylic andsulfonic acids which are capable of forming salts with alkali metals orwith organic bases, e.g., acrylic acid, 3-butenoic acid, 4-pentenoicacid, 2-hexenoic acid, ethyleneglycolacrylate succinate,ethyleneglycolacrylate phthalate, acrylamidoglycolic acid,2-acrylamido-2-2-methyl propane sulfonic acid, N-acryloyl-2-methylalanine, corresponding anhydrides and mixtures thereof. In a preferredcomposition, described further below, acrylic acid is utilized for theorganic acid monomer component of both particle and aqueous phasepolymers.

The organic ester monomers that may be considered for use, alone or incombination, for either the particle phase or the aqueous phase of thepresent invention include vinyl acetate, acrylates and methacrylates.Examples of the acrylates include methyl acrylate, ethyl acrylate,propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate,octyl acrylate, t-octyl acrylate, 2-methoxyethyl acrylate, 2-butoxyethylacrylate, 2-phenoxyethyl acrylate, chloroethyl acrylate, cyanoethylacrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzylacrylate, furfuryl acrylate, phenyl acrylate, and the like. Examples ofmethacrylate include methyl methacrylate, ethyl methacrylate, propylmethacrylate, isopropyl methacrylate, amyl methacrylate, hexylmethacrylate, cyclohexylmethacrylate, benzyl methacrylate,cyanoacetoxyethyl methacrylate, chlorobenzyl methacrylate, octylmethacrylate, N-ethyl-N-phenylamino-ethyl methacrylate, 2-methoxyethylmethacrylate,2-(3-phenylpropyloxy)ethylmethacrylate,dimethylamino-phenoxyethylmethacrylate,furfuryl methacrylate, phenyl methacrylate, cresyl methacrylate,naphthyl methacrylate, and the like. In a preferred composition,described further below, butyl acrylate is utilized in both particle andaqueous phase polymers. Hydrophobic organic monomers that are capable ofproducing "rubbery" polymers, such as butadiene and isoprene, may beconsidered as substantially equivalent substitutes for the organic estermonomers.

In the polymerization of the particle phase, minor amounts ofcrosslinker may be used, and thereby incorporated into the particlephase. Examples of crosslinkers that may be utilized in the presentinvention are ethylene glycol diacrylate, ethylene glycoldimethacrylate, butanediol dimethacrylate, methylene-bis-acrylamide,bisphenol A dimethacrylate, bisphenol A diacrylate, pentaerythritoltriacrylate, pentaerythritol tetramethacrylate, pentaerythritoltetraacrylate, glycerol tris(acryloxypropylether), bisacrylamidoaceticacid, allyl acrylate, allyl methacrylate, diallyl phthalate, diallylmaleate, and diallyl fumarate. Whether crosslinker is utilized and inwhat concentrations will depend on the particular applications of thecomposition. For diffusion transfer products, the particle phase willcomprise crosslinker in amounts generally less than 0.7% (by weight). Inthis regard, the insolubility of the particle phase in the aqueous phasewill be in greater part afforded by the hydrophobicity provided by theorganic ester monomers used for particle phase copolymer and their ratiowith the particle phase organic acid monomer. Crosslinking agents mayalso be considered for crosslinking during coating, examples includingbutanediol diepoxide, hexamethoxymethylene melamine, and cyclohexanediol diglycidyl ether.

While the inventors do not wish to be limited to any theory inexplanation of the functionality of the compositions of the presentinvention, it is believed that the unexpected stability of the two-phaseacidic aqueous composition is effected by the comparatively highconcentration of organic acid monomer units in the particle phasecopolymer. The acid constituents of the high-acid particle phase areable to intimately associate with the acid components of the aqueousphase polymers at an "aqueous/particle phase interface". In this regard,it is believed that predominantly acidic blocks of the particle phasecopolymer outwardly radiate from the particle phase, or alternatively,that the particle phase is formed with a comparatively acid-richperiphery effectuating good compatibility with the aqueous phasepolymers. In either case, the particle phase is "anchored" within thecontinuous aqueous matrix. When incorporated into a diffusion transferproduct as a neutralization layer, indication of the high-acid particlephase and the condition of "intimate association" existing in thecomposition may be visualized (or otherwise detected) as a discretecomponent having a "fuzzy", irregular, or variegated periphery. Acidpartitioning tests may be used to confirm the composition of theparticle phase.

When incorporated into diffusion transfer products, the compositionalconfiguration resulting from the high-acid particles are also believedto account for the improved cud performance. The configuration providesa more efficient stress dispersing (energy dissipating) mechanismbetween the aqueous and particle phases, effectively reducing the dryflow properties effecting curl in conventional aqueous-based film.

In a preferred composition according to the present invention, bothaqueous and particle phases of the composition comprise copolymers ofrecurring units of acrylic acid and butyl acrylate. In the preferredcomposition, the ratio of total acrylic acid (AA) to total butylacrylate (BuA) is approximately 50:50. The particle phase copolymer,comprising approximately 2/3 of total polymer, has the polymericmolecular formula --(CH₂ CHCOOH)_(X) --(CH₂ CHCOOCH₂ CH₂ CH₂ CH₃)_(Y),wherein X is approximately 30% (by weight) and Y is approximately 70%(by weight). The aqueous phase copolymer, comprising approximately 1/3of total polymer, has the same polymeric molecular formula, but whereinX is approximately 90% (by weight) and Y is approximately 10% (byweight). It will be appreciated that the AA:BuA ratios are approximateand should not be construed narrowly, but with reference to the totalityof the description herein. Variations in compositions synthesized underdifferent methods are to be expected. Reference may be made to Table 1A,infra, for representative examples of 50:50 AA:BuA two-phasecompositions.

While the 50:50 AA:BuA two-phase compositions are preferred, otheroperative two-phase compositions have been synthesized having differenttotal AA:BuA ratios. Table 1B, infra, presents representative examplesof several 60:40 AA:BuA two-phase compositions. Table 1C, infra, presentseveral representative examples of two-phase compositions with AA:BuAratios ranging from 20:80 to 40:60. In accord with the presentinvention, it will be appreciated (from observation of the datapresented in each Table) that each two-phase composition may becharacterized by its high-acid particle phase and by its organic acidcontaining aqueous phase. With regard to applications for diffusiontransfer products, curl data for representative examples of two-phasecompositions are provided in Table 2, infra.

The polymers of the instant invention may be prepared, for example, byknown emulsion polymerization techniques. Such techniques and materialssuch as initiators, emulsifiers, etc., are disclosed in severalaccessible references, such as W. R. Sorenson and T. W. Campbell,Preparative Methods of Polymer Chemistry, 2nd Ed., NY, N.Y., Wiley(1968), and M. P. Stevens, Polymer Chemistry--An Introduction, AddisonWesley Publishing Co., Reading, Mass. (1975).

For diffusion transfer products or like applications, conventionalsyntheses are, under certain conditions, difficult to implement on apractical industrial scale due to the formation of "microaggregates"often accompanying certain syntheses of the two-phase acidic aqueouscomposition. Microaggregates are formed by the aggregation ofunstabilized polymeric particles of the particle phase. The formation ofmicroaggregates is especially pronounced in emulsion polymerizationmethods involving the simultaneous synthesis of both particle andaqueous phases. It is believed that during simultaneous synthesisprocedures, the relatively high amounts of aqueous polymer formedcontinuously during synthesis act as flocculants that destabilize thepolymeric particles. Formation of high-levels of microaggregates,complicates and increases the costs of manufacture, by forcingadditional microaggregate extraction steps, such as filtration orcentrifugation. Failure to remove large microaggregates will complicate,frustrate, or otherwise foul the deposition (e.g., coating) of thecomposition as a layer in a diffusion transfer product.

Accordingly, when a neutralization layer for a diffusion transferproduct is the desired application of the two-phase high-acid aqueouscomposition, manufacture is preferably accomplished through an inventiveprocess wherein a colloidal stabilizer is utilized in an initial step asa means to reduce the formation of microaggregates by stabilizing theparticles of the particle phase throughout their synthesis. Severalembodiments of the process are provided herein.

In a first embodiment of the inventive method, a process is providedinvolving the polymerization of high-acid particles in a colloidalstabilizer. The high-acid particle phase is subsequently "blended" withan aqueous linear homopolymeric acid to form the aqueous phase.Colloidal stabilizers that may be used in this embodiment are linear,preferably partially-neutralized, polymeric acids, includingcommercially-available, linear, partially-neutralized polymeric acids.For most purposes, the suggested colloidal stabilizer is ISX 1690, alinear poly(acrylic acid) marketed by BF Goodrich having a molecularweight (weight average) of approximately 60,000. With regard to theaqueous phase homopolymeric acid, a linear polymeric acid may beutilized. The suggested linear polymeric acid is Goodrite K702, a linearpoly(acrylic acid) marketed by BF Goodrich having a molecular weight(weight average) of approximately 240,000 and having sufficient NaOHadded to neutralize approximately 2% of the carboxyl groups. It will beappreciated that the linear polymeric acid of the aqueous phase shouldgenerally have a higher molecular weight average than the linearpolymeric acid utilized as the colloidal stabilizer. Although in certainembodiments K702 may be utilized for the colloidel stabilizer, fordiffusion transfer product applications, under certain conditions, K702usage results in more microaggregate formation than ISX 1690. Synthesisof the high-acid particle phase is accomplished by means of a monomerfeed having organic acid monomers and organic ester monomers inconcentrations appropriate for formation of the desired high-acidparticle phase, together with minor concentrations of a crosslinker.Copolymerization is initiated by the use of initiators such as potassiumpersulfate and ammonium persulfate, the latter being preferred.Reference is made to Example 1-6, infra, for representative examples ofthis "blending" process.

In a second embodiment of the inventive method, a process is providedinvolving polymerization of the colloidal stabilizer "in situ" fromorganic acid monomers, followed by a simultaneous synthesis of theparticle and aqueous phase polymers. While microaggregate formation ishigher than the aforementioned "blending" process, advantage is gainedby the use of a single reactor and the removal of any reliance oncommercial sources of polymeric components. Simultaneous synthesis isaccomplished by means of a single monomer feed having organic acidmonomers and organic ester monomers in concentrations appropriate forformation of the desired two-phase acidic aqueous composition togetherwith the optional use of minor concentrations of a crosslinker tocontrol gross coagulum formation. It will be appreciated thatsurfactants may be used together with the monomer feed charge to reducemicroaggregate levels. Copolymerization is initiated by the use ofinitiators such as potassium persulfate and ammonium persulfate, thelatter being preferred. Reference is made to Example 7-9, 14, infra, forrepresentative examples of this method of "in-situ synthesis".

In a third embodiment of the inventive method, a process is providedinvolving the polymerization of the colloidal stabilizer "in situ" fromorganic acid monomers, followed by a step-wise synthesis of the particlephase and aqueous phase polymers. The "step-wise" synthesis of the thirdembodiment involves two-monomer feeds. The first monomer feed isdesigned to form the particle phase and follows in essence the particlephase synthesis of the "blending" process. The second monomer feed isdesigned to form the aqueous phase, and generally involves havingorganic acid monomers in concentrations suitable for formation of thedesired two-phase acidic aqueous composition, with consideration of theconcentrations used for the preceding particle phase synthesis.Reference is made to Example 10, infra, for a representative example ofthis "multi-staged, continuous synthesis".

In the third embodiment, while capable of producing a two-phase acidicaqueous composition virtually without formation of microaggregates,"coagulum" was formed under certain handling conditions. In contrast tomicroaggregates, it is believed that formation of such coagulum (whichhas a skin-like appearance) results from an excess of polymer incombination with foaming during fluid handling. Skin-like coagulum isgenerally undesirable for compositions used as neutralization layers fordiffusion transfer products. To prevent the formation of skin-likecoagulum without increasing microaggregate formation, the thirdembodiment (i.e., the "multi-staged continuous synthesis") may bemodified by extending the duration of the second monomer feed. In thisregard, the second monomer feed of the "unextended" embodiment willgenerally proceed for under an hour. In contrast, in the "extended"embodiment, the second monomer feed is prolonged for several hours.Under one theory, basis for the reduced formation of skin-like coagulumhas been tied to decreasing molecular weight trends observed in longermonomer feeds. Reference is made to Examples 11-13, infra, forrepresentative examples of this "extended, multi-staged continuoussynthesis".

Regardless of the method utilized, two-phase acidic aqueous compositionsare especially well suited for incorporation into diffusion transferproducts as a neutralization layer. As to this application, Table 3,infra, provides post-process pH results of several two-phase acidicaqueous composition samples.

The neutralization layers comprising the two-phase acidic aqueouscompositions of this invention can be incorporated into diffusiontransfer products, for example, in image-receiving elements designed toreceive and mordant image dye-providing materials. Such image-receivingelements (described in further detail below) will generally comprise asuitable support carrying a neutralization layer of this invention andmay also include an image-receiving layer comprising any variety ofmordant species or mixture thereof. In this regard, various polymericmaterials have been utilized as mordants in photographic products andprocesses including those of the diffusion transfer type. Thus,polymeric mordants suited to application in diffusion transfer productsand processes for the formation of photographic images in dye aredescribed, for example, in U.S. Pat. Nos. 3,148,061 (issued Sep. 8, 1964to H. C. Haas); 3,758,445 (issued Sep. 11, 1973 to H. L. Cohen et at.);3,770,439 (issued Nov. 6, 1973 to L. D. Taylor); 3,898,088 (issued Aug.5, 1975 to H. L. Cohen, et at.); 4,080,346 (issued Mar. 31, 1978 to S.F. Bedell); 4,308,335 (issued Dec. 29, 1981 to T. Yamamoto, et at.);4,322,489 (issued to E. H. Land, et at.) and 4,563,411 (issued Jan. 7,1986 to I. Y. Bronstein-Bonte), and 4,794,067 (issued Dec. 27, 1988 toJ. M. Grashoff, et at.).

Referring to FIG. 1, there is shown an image-receiving element 10comprising support material 12, a neutralizing system 14 incorporating atwo-phase acidic aqueous composition according to the present invention,a timing layer 16, an image-receiving layer 18, and an overcoat layer20. Support material 12 can comprise any variety of materials capable ofcarrying neutralizing system 14 and the other layers as shown in FIG. 1.Paper, vinyl chloride polymers, polyamides such as nylon, polyesterssuch as polyethylene glycol terephthalate or cellulosic derivatives suchas cellulose acetate or cellulose acetate-butyrate can be suitablyemployed. It will be appreciated that depending upon the particularapplication intended for image-receiving element 10, the nature ofsupport material 12 as a transparent, opaque or translucent materialwill be a matter of choice.

As indicated previously, support 12 of image-receiving element orarticle 10 can be transparent, opaque or translucent depending upon theparticular application of the element or article. Thus, whereimage-receiving element 10 is desirably utilized in the manufacture ofphotographic diffusion transfer film units such as shown generally inFIGS. 2 and 3 hereof, where the desired image will be viewed through asupport, support 12 will be of transparent material. A preferredmaterial for this purpose is a polyethylene glycol terephthalatesheetlike support material. Alternatively, where image-receiving element10 is utilized in the manufacture of a photographic film unit such as isgenerally shown in FIG. 4, where the desired image will be viewed as areflection against a light-reflecting layer, support material 12 willpreferably be of opaque material.

In FIG. 1 is shown overcoat layer 20 which comprises an optional layerof image-receiving element 10. Image-receiving layer 18 can, thus,comprise the outermost layer of image-receiving element 10. In someinstances, it may be desirable to provide image-receiving layer 18 witha washing treatment, as by washing the layer with ammonia or a solutionof ammonium hydroxide in a concentration, preferably of from about 2% toabout 8% by weight. Such ammonia washing treatment effectivelyneutralizes residual acrolein/formaldehyde condensate where suchmaterial is utilized for the hardening of the image-receiving layer andfor the provision of reduced water sensitivity. According to oneembodiment of the invention, overcoat layer 20 can comprise a polymericmaterial such as polyvinyl alcohol.

Overcoat layer 20 can also be utilized as a means of facilitatingseparation of image-receiving element 10 from a photosensitive element.Thus, where the image-receiving element is utilized in a photographicfilm unit which is processed by distribution of an aqueous alkalineprocessing composition between the image-receiving element and aphotoexposed photosensitive element and is adapted, after formation of adye image, to separation from the developed photosensitive element andthe processing composition, overcoat layer 20 can effectively functionas a "strip coat".

A suitable "strip coat" can be prepared from a hydrophilic colloidmaterial such as gum arabic or the like. For example, overcoat 20 cancomprise a solution of hydrophilic colloid and ammonia and can be coatedfrom an aqueous coating solution prepared by diluting concentratedammonium hydroxide (about 28.7% NH₃) with water to the desiredconcentration, preferably from about 2% to about 8% by weight, and thenadding to this solution an aqueous hydrophilic colloid solution having atotal solids concentration in the range of about 1% to about 5% byweight. The coating solution also preferably may include a small amountof surfactant, for example, less than 0.10% by weight of Triton X-100(Rohm and Haas Co., Phila., Pa.). A preferred solution comprises about 3parts by weight of ammonium hydroxide and about 2 parts by weight of gumarabic.

Overcoat 20 can also be used as a means of decolorizing optical filteragent typically employed in a photographic processing composition. Apolymeric layer 20 is provided over image-receiving layer 18 of animage-receiving element intended for use in a film unit of the integralnegative-positive type, described in detail hereinafter. Thedecolorizing overcoat layer 20 serves to increase the apparent whitenessof the layer of processing composition providing the background againstwhich the image is viewed. Suitable polymeric decolorizing materials foruse as layer 20 are described in U.S. Pat. Nos. 4,298,674 (issued Nov.3, 1911 to E. H. Land, et at.); 4,294,907 (issued Oct. 13, 1981 to I. Y.Bronstein-Bonte, et at.); 4,367,277 (issued Jan. 4, 1983 to C. K.Chiklis, et at.), and U.S. Pat. No. 4,777,112 (issued Oct. 11, 1988 toG. S. La Pointe, et at.).

The image-receiving layers incorporating the neutralizing systemsaccording to the present invention find applicability in a number ofphotographic diffusion transfer products and processes. According to oneembodiment of the present invention, the image-receiving layers of theinvention are utilized in photographic film units adapted to theprovision of photographs comprising the developed silver halideemulsion(s) retained as part of a permanent laminate, with the desiredimage being viewed through a transparent support against a reflectingbackground. In such photographs, the image-carrying layer is notseparated from the developed silver halide emulsion(s). Diffusiontransfer photographic products providing an image viewable withoutseparation against a reflecting background in such a laminate have beenreferred to in the art as "integral negative-positive film units".

Integral negative-positive film units of a first type are described, forexample, in the above noted U.S. Pat. No. 3,415,644 and includeappropriate photosensitive layer(s) and image dye-providing materialscarried on an opaque support, an image-receiving layer carried on atransparent support and means for distributing a processing compositionbetween the elements of the film unit. Photoexposure is made through thetransparent support carrying polymeric acid-reacting layer, a timinglayer and the image receiving-layer of the invention. A processingcomposition containing a reflecting pigment is distributed between theimage-receiving and photosensitive components. After distribution of theprocessing composition and before processing is complete, the film unitcan be, and usually is, transported into light. Accordingly, in integralnegative-positive film units of this type, the layer provided bydistributing the reflecting pigment provides a reflecting background forviewing through the transparent support the image transferred to theimage-receiving layer.

Integral negative-positive film units of a second type are described,for example, in U.S. Pat. No. 3,594,165, include a transparent support,carrying the appropriate photosensitive layers and associated imagedye-providing materials, a permeable opaque layer, a permeable andpreformed light-reflecting layer, and means for distributing aprocessing composition between the photosensitive layer and atransparent cover or spreader sheet carrying a polymeric acid-reactinglayer and a timing layer. Integral negative-positive film units of thissecond type include an opaque processing composition which isdistributed after photoexposure to provide a second opaque layer whichcan prevent additional exposure of the photosensitive element. In filmunits of this second type, exposure is made through the transparentcover or spreader sheet. The desired transfer image is viewed againstthe reflecting pigment-containing layer through the transparent supportelement.

The arrangement and order of the individual layers of the diffusiontransfer film units described herein may vary in many ways as known inthe art. For convenience, however, the more specific descriptions of theinventive application hereinafter set forth will be by use of dyedeveloper diffusion transfer film units of the types generallycontemplated in previously mentioned patents. Thus, details relating tointegral negative-positive film units of the first type describedhereinbefore can be found in such patents as U.S. Pat. Nos. 3,415,644and 3,647,437 while details of the second type are found in U.S. Pat.No. 3,594,165. It will be readily apparent from such descriptions thatother image-forming reagents may be used, e.g., color couplers, couplingdyes, or compounds which release a diffusible dye or dye intermediate asa result of coupling or oxidation.

Referring now to the drawings, FIG. 2 shows a film unit of the typedescribed in referenced U.S. Pat. Nos. 3,415,644 and 3,657,437,following exposure and processing. The film unit 30 includes animage-beating layer 38, timing layer 36, and neutralizing system 34incorporating a two-phase acidic aqueous composition according to thepresent invention. After photoexposure of photosensitive layer(s) 42(through transparent support 32, neutralizing system 34, timing layer36, and image-beating layer 38) the processing composition retained in arupturable container (not shown) is distributed between layers 38 and42. Processing compositions used in such film units of the presentinvention are aqueous alkaline photographic processing compositionscomprising a reflecting pigment, usually titanium dioxide, and apolymeric film-forming agent and will preferably contain an opticalfilter agent described in detail in U.S. Pat. Nos. 3,647,437 and4,680,247.

Distribution of the processing composition over photoexposed portions ofphotosensitive system 42 provides a light-reflecting layer 40 betweenimage-bearing layer 38 and photosensitive layer(s). This layer, at leastduring processing, provides sufficient opacity to protect photosensitivesystem 42 from further photoexposure through transparent support 32. Asreflective layer 40 is installed, by application of the processingcomposition, development of photoexposed photosensitive layer(s) 42 isinitiated to establish in manners well-known in the art an imagewisedistribution of diffusible image-providing material which can comprisesoluble silver complex or one or more dye or dye intermediateimage-providing materials. The diffusible image-providing materials istransferred through permeable, light reflecting layer 40 where it ismordanted, precipitated or otherwise retained in or on image-bearinglayer 38. The resulting transfer image is viewed through transparentsupport 32 against light-reflecting layer 40.

The light-reflecting layer 40 provided by the embodiment of theinvention shown in FIG. 2 is formed by solidification of the stratum ofthe processing composition distributed after exposure. The processingcomposition will include the film-forming polymer which provides thepolymeric binder matrix for the light-reflecting pigment of layer 40.Absorption of water from the applied layer of processing compositionresults in a solidified film comprising the polymeric binder matrix andthe pigment material, thus providing the light reflecting layer 40 whichpermits the viewing there against of image 38 through transparentsupport 32. In addition, light-reflecting layer 38 serves to laminatetogether the developed photosensitive system 42 and the image-bearinglayer 38 to provide the final photographic laminate.

In order to ensure that pH reduction effected by the two-phase acidicaqueous neutralizing system occurs after a sufficient, predeterminedperiod and not prematurely so as to interfere with the developmentprocess, the neutralizing system preferably is associated with a timinglayer 16 ("diffusion control time modulating layer"). Ideally, this timemodulating layer should initially be impermeable to alkali and then,after a brief predetermined period, should allow alkali to penetrate itreadily to be depleted by the neutralizing system and thereby shut-downthe development process.

Accordingly, in each of the articles shown in FIGS. 1 to 4 is shown atiming layer which is included for the control of the pH-reducingproperties of the neutralizing system according to embodiments of thepresent invention. Thus, there is shown in FIG. 2 timing layer 36positioned between neutralizing system 34 and image-bearing layer 38.The timing layer will typically be comprised of polyvinyl alcohol,gelatin or other polymer through which the alkali may diffuse to theneutralizing system. The presence of such timing layer between theimage-receiving layer 38 and the acid-reacting layer 34 effectivelycontrols the initiation and the rate of capture of alkali by the acidreacting layers and the advantages thereof in diffusion transfer systemsare described with particularity in U.S. Pat. Nos. 3,362,819; 3,419,389;3,421,893; 3,455,686; 3,577,237, and 3,575,701.

In the film unit shown in FIG. 2, neutralizing system 34 and the timinglayer 36 are shown on transparent support 32. If desired, layers 34 and36 can be positioned between opaque support 44 and photosensitivelayer(s) 42. Thus, neutralizing system 34 can be positioned on opaquesupport 44 and timing layer 36 can be positioned on the neutralizingsystem. In turn, the emulsion layer(s) comprising photosensitive 42 canbe positioned on the timing layer. In this case, image-receiving element32a will comprise transparent support, and directly thereon,image-bearing layer 38. For reference, the utilization of previouspolymeric acid-reacting layers and timing layers in a photosensitiveelement is described in U.S. Pat. Nos. 3,362,821 and 3,573,043.

In accordance with an embodiment of the invention, a photographic filmunit can comprise a temporary laminate including the several layers ofthe photographic film unit confined between two dimensionally stablesupports and having the bond between a predetermined pair of layersbeing weaker than the bond between other pairs of layers. Thus, withreference to FIG. 2, an image-receiving element 32a, comprisingtransparent support 32, neutralizing system 34, timing layer 36, andcorresponding generally to image-receiving element 10 of FIG. 1, can bearranged in article 30 such that image-receiving layer 38 is temporarilybonded to the silver halide emulsion layer 42 prior to exposure. Therupturable container or pod (not shown) can then be positioned suchthat, upon its rupture, the processing composition will delaminate thetemporary bond and be distributed between the aforesaid layers 38 and42. The distributed layer of processing composition upon drying formslight-reflecting layer 40 which serves to bond the layers together toform the desired permanent laminate. Procedures for forming suchprelaminated film unit, i.e., film units in which the several elementsare temporarily laminated together prior to exposure, are described, forexample, in U.S. Pat. No. 3,652,281, issued to Albert J. Bachelder andFrederick J. Binda on Mar. 28, 1972, and U.S. Pat. No. 3,652,282, issuedto Edwin H. Land on even date. A particularly useful and preferredprelamination utilizes a water-soluble polyethylene glycol as describesand claimed in U.S. Pat. No. 3,793,023, issued Feb. 19, 1974 to Edwin H.Land.

If desired, the film unit shown in FIG. 2 may utilize a transparentsupport instead of the opaque support 44 shown therein. In accordancewith this alternative embodiment, an opaque layer, e.g.,pressure-sensitive, should be superposed over said transparent supportto avoid further exposure through the back of the film unit duringprocessing outside of the camera. In the embodiment illustrated in FIG.2, photoexposure is effected through the image-receiving element. Whilethis is a particularly useful and preferred embodiment, it will beunderstood that the image-receiving element may be initially positionedout of the exposure path and superposed upon the photosensitive elementafter photoexposure, in which event the processing and final imagestages would be the same as in FIG. 2.

In FIG. 3 is shown, following exposure and processing, a second integralnegative-positive type of diffusion transfer film unit utilizing andarrangement of elements generally described in U.S. Pat. No. 3,594,165and British Pat. No. 1,330,524. Such arrangement provides an integralnegative-positive reflection print and photoexposure and viewing areeffected from opposite sides. Film unit 50 includes a processingcomposition initially retained in a rupturable container (not shown)arranged to distribute the processing composition between thephotosensitive system or layer 66 and a cover or spreader sheet 68acomprising a transparent sheet material 68, a neutralizing system 66according to the present invention and a timing layer 64. Spreader sheet68a facilitates uniform distribution of processing composition afterphotoexposure of photosensitive system or layer 60 which is effectedthrough transparent sheet material 68. Processing compositions used insuch film units are aqueous, alkaline photographic processingcompositions which include a light absorbing opacifying agent, e.g.,carbon black.

Distribution of the processing composition between photoexposedphotosensitive system or layer 60 and spreader sheet 68a installs anopaque layer 62 which protects system or layer 60 from furtherphotoexposure through transparent spreader sheet 68a. Like the filmunits of FIG. 3, as and after opaque layer 62 is installed, theprocessing composition initiates development of photoexposedphotosensitive system or layer 60 to establish an imagewise distributionof diffusible image-providing materials in manners well-known to theart. For example, the processing composition may contain developingagents sufficient to effect photographic development. Alternatively,developing agents may be present in one or more layers of the film unitso that they may be carded to system or layer 60 by the processingcomposition. The diffusible imagewise distribution is transferred toimage-receiving layer 54 through permeable light-reflecting layer 56which comprises a preformed layer including a light-reflecting pigment.Film units of the type shown in FIG. 3 may also comprise a preformed andpermeable opaque layer 58 including a light-absorbing pigment, e.g., adispersion of carbon black in a polymer permeable to processingcomposition. Such layer, between photosensitive system or layer 60 andlight-reflecting layer 56, permits in-light development of film unit 50,providing opacification for the protection of photoexposedphotosensitive system or layer 60 against further exposure throughtransparent support 52 and layers 54 and 56. The transferred image isviewed through transparent support 52 against light-reflecting layer 56.

In further embodiments, two-phase acidic aqueous compositions of thepresent invention can be utilized in neutralizing systems for so-called"peel apart" diffusion transfer film units designed to be separatedafter processing. Such a diffusion transfer film unit of the inventionis shown in FIG. 4 as film unit 70. The film unit shown in FIG. 4comprises a photosensitive element comprising an opaque support 72carrying a photosensitive layer or system 74. In film units of thistype, the photosensitive layer or system 74 is photoexposed and aprocessing composition 76 is then distributed over the photoexposedlayer or system 74. An image-receiving element 86a, correspondinggenerally to image-receiving element 10 of FIG. 1, is superposed on thephotoexposed photosensitive element 74. As shown in FIG. 4,image-receiving element 86a comprises an opaque support material 88, anda light reflecting layer 86; against which the desired transfer image inviewed and which typically will comprise a polymeric matrix containing asuitable white pigment material, e.g., titanium dioxide. A neutralizingsystem 84 according to the present invention is shown positioned onlight-reflecting layer 86 on which is shown timing layer 82, theimage-receiving layer 80 of the invention and, in turn, overcoat layer78, each of which layers is comprised of materials describedhereinbefore in connection with the articles of film units shown inFIGS. 1 to 3. Like the film units shown in FIGS. 2 and 3, the processingcomposition permeates photoexposed photosensitive layer or system 74 toprovide an imagewise distribution of diffusible dye image-providingmaterial which is transferred at least in part to image-receiving layer78. Unlike the film units of FIGS. 2 and 3, however, the transferred dyeimage is viewed in image-bearing layer 80 against light-reflecting layer66 after separation of image-receiving element 86a from photosensitiveelement 7a.

While support material 88 of image-receiving element 86a is shown asbeing of opaque material, it will be appreciated that a transparentsupport material can be employed and that the film unit can be processedin the dark or an opaque sheet (not shown), preferablypressure-sensitive, can be applied over such transparent support topermit in-light development. In accordance with an embodiment of theinvention, whereby a reflection print is provided upon separation ofimage-receiving element 86a from photosensitive element 72a, opaquesupport 88 and light-reflecting layer 86, will comprise, for example, asuitable paper support, coated, preferably on both sides, with apolymeric coating, e.g., polyethylene, pigmented with titanium dioxide.Such a support material can be suitably provided with neutralizingsystem 84 according to an embodiment of the present invention, a timinglayer 82, an image-bearing layer 80, and an optional overcoat layer 78,as shown in FIG. 4 with formation of image-receiving element 86a.

It will be appreciated that, where a transparency is desirably providedfrom a film unit 70 of FIG. 4, support 88 can be transparent and lightreflecting layer 86 omitted. The desired image in image-bearing layer 80can then, upon separation of image-receiving element 86a fromphotosensitive element 72a, be viewed as a positive transparency throughtransparent support material 88.

The film units illustrated in FIGS. 2 to 4 have, for convenience beenshown as monochrome films. Multicolor images may be obtained byproviding the requisite number of differentially exposable silver halideemulsions, and said silver halide emulsions are most commonly providedas individual layers coated in superposed relationship. Film unitsintended to provide multicolor images comprise two or more selectivelysensitized silver halide layers each having associated therewith anappropriate image dye-providing material providing an image dye havingspectral absorption characteristics substantially complementary to thelight by which the associated silver halide is exposed. The mostcommonly employed negative components for forming multicolor images areof the "tripack" structure and contain blue-, green- and red-sensitivesilver halide layers each having associated therewith in the same or ina contiguous layer a yellow, a magenta and a cyan image dye-providingmaterial, respectively. Interlayers or spacer layers may, if desired, beprovided between the respective silver halide layers and associatedimage dye-providing materials or between other layers. Integralmulticolor photosensitive elements of this general type are disclosed inU.S. Pat. No. 3,345,163, issued Oct. 3, 1967, to Edwin H. Land andHoward G. Rogers, as well as in the previously noted U.S. Patents, e.g.,in FIG., 9 of the aforementioned U.S. Pat. No. 2,983,606.

The image dye-providing materials which may be employed in suchprocesses generally may be characterized as either (1) initially solubleor diffusible in the processing composition, but are selectivelyrendered non-diffusible in an imagewise pattern as a function ofdevelopment; or (2) initially insoluble or non-diffusible in theprocessing composition, but which are selectively rendered diffusible orprovide a diffusible product in an imagewise pattern as a function ofdevelopment. These materials may be complete dyes or dye intermediates,e.g., color couplers. The requisite differential in mobility orsolubility may, for example, be obtained by a chemical action such as aredox reaction or a coupling reaction.

As examples, of initially soluble or diffusible materials and theirapplications in color diffusion transfer, mention may be made of thosedisclosed, for example, in U.S. Pats. Nos. 2,774,668; 2,968,554;2,983,606; 2,087,817; 3,185,567; 3,230,082; 3,345,163, and 3,443,943. Asexamples of initially non-diffusible materials and their use in colortransfer system, mention may be made of the materials and systems,disclosed in U.S. Pat. Nos. 3,185,567; 3,443,939; 3,443,940; 3,227,550,and 3,227,552. Both types of image dye-providing substances and filmunits useful therewith also are discussed in U.S. Pat. No. 3,647,437 towhich reference may be made.

In addition to the above description of the layers comprising theseveral diffusion transfer product and process embodiments illustratedin FIGS. 1 to 4, an optional barrier layer (not shown) may also beutilized. In this regard, and depending on composition, such barrierlayers can function simply as spatial separators or they can providespecified time delays by swelling at controlled rates or undergoingreactions such as hydrolysis or dissolution. In general, the barrierlayer, if utilized together with the present invention, should typicallybe deposited over the neutralizing system to minimize the sink-in of thetiming layer and the transfer of water from the timing layer andnegative during deposition. Such barrier layer is typically designed tomaintain a surface pH of approximately 5 for 2-3 minutes in contact withwater, yet `open` rapidly at high pH to allow neutralization of thealkaline reagent after processing. One commercially availablecomposition that may be considered for use as a barrier layer is DOWPRIMACOR 5890 (ethylene-acrylic acid copolymer, 20 wt % AA). Othercompositions may be selected based on desired functionality and/orcompatibility.

The polymeric neutralizing system can be deposited at any amount whichis effective for the intended purpose. Preferably, it is deposited at athickness on the order of 0.3 to 1.5 mil. and at a coverage in the rangeof 13.5 to 22.5 milliequivalents acid/ft², depending upon the alkalicontent of the activator which is to be neutralized.

The following examples are provided to further illustrate the invention.Unless otherwise noted, microaggregate concentrations were measured on a45 μm nominal size filter.

EXAMPLES Reference Example A

A two-phase high-acid aqueous composition (60:40 AA:BuA) was preparedthrough the simultaneous synthesis of both aqueous and particle phases.The resulting composition had microaggregates in amounts undesirable forphotographic applications.

More specifically, in a 12 l round bottom flask with a stirrer set at280 rpm, 6209.9 g distilled water was heated to 80° C. while deaerating.A 147.6 g seed was taken from an AA:BuA monomer mix and charged into thereactor. The AA:BuA monomer mix was prepared from 1768.3 g acrylic acid,1176.4 g butyl acrylate, and 7.9 g divinyl benzene. After mixing thereactor solution charged with the seed for 10 minutes, a solution of29.15 g ammonium persulfate in 713.8 g distilled water was added over 15minutes. The remaining AA:BuA monomer mix was then gradually fed intothe reactor over a period of 180 minutes (feed rate 16.7 ml/min.). Atthe end of the feed, the solution was held at 80° C. for 30 minutes,then cooled to 50° C. 8.3 g t-butyl peroxybenzoate was added, followedby 4.4 g sodium bisulfite in 71.4 g distilled water. The solution washeld at 50° C. for 60 minutes. Analysis of the two-phase high-acidaqueous composition revealed a comparatively high microaggregateconcentration of 0.3466%.

Reference Examples B

Several two-phase high-acid aqueous composition were prepared throughthe simultaneous synthesis of both aqueous and particle phases. Thesynthesis for each composition followed in essence the process ofReference Example A, but with certain modifications. For the synthesisof one composition, potassium-styrene-sulfonate was charged into thereactor flask prior to the addition of the AA:BuA monomer mix. For thesynthesis of another composition, acrylamido-2-methyl-1-propanesulfonicacid (AMPS) was fed simultaneously with the AA:BuA monomer mix. Inanother synthesis, the AMPS modified process was further refined by theuse of a Dialyzed Dowfax 2A1 (Dowfed) surfactant (from Dow Chemical Co.)in the seed. Analysis of compositions from thepotassium-styrene-sulfonate modified process, the AMPS modified process,and the AMPS/Dowfad modified process revealed comparatively highmicroaggregate concentrations of 0.6467%, 0.18%, 0.42%, respectively.

Reference Example C

A two-phase high-acid aqueous composition (50:50 AA:BuA) was preparedthrough the simultaneous synthesis of both aqueous and particle phases.The synthesis followed in essence the process of Reference Example A.(The AA:BuA monomer mix was prepared from 606.0 g acrylic acid, 609.5 gbutyl acrylate, and 4.1 g divinyl benzene). However, a neutralizedlinear poly(acrylic acid) (Goodrite K702, from BF Goodrich) was added asa colloidal stabilizer in the initial distilled water (2691.3 g) charge.Analysis of the resulting composition revealed a microaggregateconcentration of 0.194%.

Example 1

A two-phase high-acid aqueous composition was prepared through a"blending" method.

More specifically, an AA:BuA monomer mix was prepared from 956 g butylacrylate, 239.3 g acrylic acid, 4.0 g divinyl benzene and 20.63 g Dowfad(from Dow Chemical Co.). A 61.0 g seed was taken from the AA:BuA monomermix and added into a 80° C. poly(acrylic acid) solution prepared from336.3 g ISX 1690 (35.7%) (linear PAA from BF Goodrich) in 2400 g ofdistilled water. The solution was stirred for 5.5 minutes at 160 rpm. Aninitiator solution prepared from 5.73 g potassium persulfate in 140 gdistilled water was added over 10.22 minutes. Stirring continued for anadditional 10 minutes. The remaining AA:BuA monomer mix was fed into thesystem over 240 minutes. After 210 minutes, the stir rate was increasedto 240 rpm. At the conclusion of the monomer feed, the system waspost-heated at 80° C. for 45 minutes, then cooled to 50° C. for over 15minutes. 3.2575 g t-butyl peroxybenzoate and 1.725 g sodium bisulfite in25 g distilled water was subsequently added. The system was post-heatedan additional 45 minutes at 50° C., stirred at 400 rpm, then allowed tocool at room temperature. Analysis of the intermediate 20:80 AA:BuAcomposition revealed the following: Solids, 32.07% (71.75% BuA; 28.84AA); Microaggregates, 0.0254 g/100 g composition (0.025%); pH 2.18;Viscosity, 530 cps (Brookfield, #3 spindle, 60 rpm). 2400 g of theintermediate 20:80 AA:BuA particle phase composition was blended with1336.8 g Goodrite K702 (25.8%) (partially neutralized linear PAA from BFGoodrich) to form the aqueous phase, bringing the composition to 50:50AA:BuA. Analysis of the resulting two-phase high-acid aqueouscomposition revealed the following: Solids, 29.44%; Microaggregates,0.0076 g/50.0 g composition (0.015%).

Example 2

A two-phase high-acid aqueous composition was prepared through a"blending" method.

More specifically, the procedure proceeded as Example 1, but incontrast, utilized the following components: the initial poly(acrylicacid) solution utilized 347.8 g ISX 1690 (34.5%) in 2400 g distilledwater; the AA:BuA monomer mix utilized 837.3 g butyl acrylate, 358.7 gacrylic acid, 4.0 g divinyl benzene and 20.63 g Dowfad (12.9%); and theinitiator solution utilized 5.73 g potassium persulfate in 140 gdistilled water. 61.0 g of the AA:BuA monomer mix was used for the seed.The system was post-heated 60 minutes at 80° C., cooled to 50° C. forover 15 minutes, sodium bisulfite and t-butyl peroxybenzoate addedthereafter, and the system subsequently post-heated 45 minutes at 50° C.Analysis of the intermediate 20:80 AA:BuA composition revealed thefollowing: Solids, 31.85%; Microaggregates, 0.0123 g/100 g composition(0.012%); pH 2.08; Viscosity, 93 cps (Brookfield, #2 spindle, 60 rpm);Coagulum, 0.0986 g. 2800 g of the intermediate 20:80 AA:BuA compositionwas blended with 936.7 g of Goodrite K702 (25.8%), bringing thecomposition to 50:50 AA:BuA. Analysis of the resulting two-phasehigh-acid aqueous composition revealed the following: Solids, 29.8%;Microaggregates, 0.0110 g/100 g composition (0.011%).

Example 3

A two-phase high-acid aqueous composition was prepared through the"blending" method of Example 1 without the use of Dowfad.

More specifically, the procedure proceeded as Example 1 with the AA:BuAmonomer mix modified to have 956.8 g butyl acrylate, 239.3 g acrylicacid, and 4.0 g divinyl benzene. 60.0 g of the AA:BuA monomer mix wasused for the seed. Analysis of the intermediate AA:BuA compositionrevealed the following: Solids, 32.37%; Microaggregates, 0.0067 g/100 gcomposition (0.006%); pH 2.26; Viscosity, 80 cps (Brookfield, #2spindle, 60 rpm); Coagulum, 0.026 g. 2320.8 g of the intermediate 20:80AA:BuA composition was blended with 1354.4 g Goodrite K702 (24.9%),bringing the composition to 50:50 AA:BuA. Analysis of the resultingtwo-phase high-acid aqueous composition revealed the following:Microaggregates, 0.0085 g/100 g composition (0.008%); Viscosity, 390 cps(Brookfield, #2 spindle, 60 rpm).

Example 4

An intermediate 20:80 AA:BuA composition was prepared according to thepertinent initial steps of Example 2 without the use of Dowfad. TheAA:BuA monomer mix was modified to have 837.3 g butyl acrylate, 358.7 gacrylic acid, and 4.0 g divinyl benzene. 60.0 g of the AA:BuA monomermix was used for the seed. Analysis of the intermediate 20:80 AA:BuAcomposition revealed the following: Solids, 32.61%, Microaggregates0.0041 g/100 g composition (0.004%), pH 2.32, Viscosity 95 cps(Brookfield, #2 spindle, 60 rpm).

Example 5

A two-phase high-acid aqueous composition was prepared through a variant"blending" process, wherein the final poly(acrylic acid) addition occursduring the latter part of the particle phase polymerization (cf."in-situ blending").

More specifically, a 5 l four-necked round bottom flask was fitted witha mechanical stirrer, thermometer, nitrogen inlet tube, monomer feedline, initiator feed line, reflux condenser, sampling tube and additionfunnel. The flask was charged with 1500.0 g distilled water and 218.8 gISX 1690 (34.4%) (linear PAA from BF Goodrich) and then heated to 79° C.while deaerating with nitrogen. The nitrogen line was placed below thesolution surface and the rate monitored by a bubble counter attached tothe outlet of the reflux condenser. The stir rate was maintained at 200rpm. When the reactor contents reached 80° C., the nitrogen line wasraised well above the solution surface 37.6 g of an AA:BuA monomer mixwas introduced into the reactor vessel. The AA:BuA monomer mix wasprepared from 60.0 g butyl acrylate, 150.0 g acrylic acid, and 2.5 gdivinyl benzene. Immediately after the addition of the seed charge, aninitiator solution was prepared by adding 3.033 g ammonium persulfateinto 88.8 g distilled water and rapidly stirred under a nitrogen blanketto effectuate dissolution 10 minutes after addition of the seed charge,the initiator solution was introduced into the reactor over 10 minutesusing a pump calibrated to deliver 9.18 cc./min. 5 minutes aftercompletion of the initiator addition, the balance of the A/BuA monomermix was fed into the reactor over 240 minutes using a pump calibrated todeliver 3.31 cc./min. Throughout, the reactor temperature was maintainedat 80° C. Three hours into the monomer feed, feed of 1430.3 g GoodriteK702 (26.2%) (partially neutralized linear PAA from BF Goodrich) wascommenced. The K702 poly(acrylic acid) was delivered over 165 minutesthrough the addition funnel calibrated to a flow rate of 8.67 cc./min.(The K702 feed generally overlapped the last hours of the monomer feedand its end coincided with the initiation of the post-heat). Followingthe monomer addition, the temperature was maintained at 80° C. for 30minutes and subsequently cooled to 50° C. for over approximately 15minutes. Once the temperature reached 50° C., 2.043 g t-butylperoxybenzoate was added through the sampling tube, followed by asolution of 1.080 g sodium metabisulfite in 12.5 g distilled water.Addition of each approximated 10 seconds. The reaction was then heatedat 50° C. for 60 minutes, then cooled to room temperature. Analysis ofthe resulting two-phase high-acid aqueous composition revealed thefollowing: Solids, 30.0%; Microaggregates, 0.0074 g/100 g composition(0.007%); pH 2.7; Viscosity, 600 cps (Brookfield, #2 spindle, 60 rpm),Coagulum, none.

Example 6

A two-phase high-acid aqueous composition was prepared through an"in-situ blending" process similar to Example 5, but wherein the finalpoly(acrylic acid) addition occurred throughout the particle phasepolymerization. Analysis of the resulting two-phase high-acid aqueouscomposition revealed the following: Solids, 26.8%; pH 2.8; Viscosity,800 cps (Brookfield, #2 spindle, 60 rpm), Coagulum, 2.3%.

Example 7

A two-phase high-acid aqueous composition (50:50 AA:BuA) was preparedaccording to an "in situ synthesis" process.

More specifically, in a 3 l reaction flask equipped with a mechanicalstirrer, reflux condenser, nitrogen inlet line, thermometer, and feedlines, 1551.3 g distilled water was heated to 80° C. while deaeratingwith nitrogen introduced into the system below water level at a flow ofapproximately 5 psi. 45 g of acrylic acid were added and followed by theaddition of an initiator solution made from 3.51 g potassium persulfatein 90 g distilled water. Allowing the polymerization of the acrylic acidseed to continue for 20 minutes, an AA:BuA monomer mix was fed into thereactor over 227.16 minutes at a feed rate of 3.5 ml/min. The AA:BuAmonomer mix was prepared from 321.3 g acrylic acid, 366.3 butylacrylate, and 2.5 g divinyl benzene. The solution was held at 80° C. foran additional 30 minutes, then cooled to 50° C. 1.99 g t-butylperoxybenzoate was added, followed by addition of 1.05 g sodiumbisulfite in 17.2 g distilled water. The solution was then held at 50°C. for a final 60 minutes. Analysis of the resulting two-phase high-acidaqueous composition revealed the following: Solids, 30.98%,Microaggregates, 0.0498 g/100 g composition (0.049%); Viscosity, 888cps. (#2 spindle, 60 rpm); Coagulation, <0.01%. Partitioning data are asfollows: Aqueous Phase Composition, 92.26:7.74 AA:BuA; Particle PhaseComposition, 25.22:74.78 AA:BuA.

Example 8

A two-phase high-acid aqueous composition (30:70 AA:BuA) was preparedaccording to an "in-situ synthesis" process, similar to Example 7.

More specifically, in a reaction flask equipped with a mechanicalstirrer (225 rpm), reflux condenser, nitrogen inlet line, thermometer,and feed lines, 2585.3 g distilled water was heated to 80° C. whiledeaerating. With the system sparged with nitrogen as Example 7, 75 g ofacrylic acid were added and followed by the addition of an initiatorsolution made from 3.32 g potassium persulfate in 150 g distilled water.At the conclusion of the "in situ" polymerization of the acrylic acidseed, an AA:BuA monomer mix was fed into the reactor over 191 minutes ata feed rate of 6.5 ml/min. The remaining steps (post-catalyst steps)followed essentially as Example 7 utilizing 3.32 g t-butylperoxybenzoate and a solution of 5.85 g potassium bisulfite in 150 gdistilled water. Analysis of the resulting two-phase high-acid aqueouscomposition revealed the following: Solids, 30.96%; Microaggregates,0.0014%; Viscosity, 75 cps (#3 spindle, 60 rpm). Partitioning data areas follows: Aqueous Phase Composition, 92.28:7.72 AA:BuA; Particle PhaseComposition, 44.49:55.51 AA:BuA.

Example 9

A two-phase high-acid aqueous composition was prepared according to an"in situ synthesis" process, similar to Examples 7 and 8, however theinitiator potassium persulfate was substituted with ammonium persulfate.

More specifically, in a 5 l reaction flask equipped with a mechanicalstirrer (200 rpm), reflux condenser, nitrogen inlet line, thermometer,and feed lines, 2705.3 g distilled water was heated to 80° C. whiledaerating. After the system was sparged with nitrogen as Example 7, 75.0g of acrylic acid were added and followed by the addition of aninitiator solution made from 4.93 g ammonium persulfate in 30.0 gdistilled water. At the conclusion of the "in situ" polymerization ofthe acrylic acid seed, an AA:BuA monomer mix was fed into the reactor ata feed rate of 5.5 ml/min. The AA:BuA monomer mix was prepared from535.5 g acrylic acid, 610.5 g butyl acrylate, and 4.2 g divinyl benzene.The remaining steps (post-catalyst steps) followed in essence Example 7,utilizing 3.32 g t-butyl peroxybenzoate and a solution of 2.18 g sodiumbisulfite in 28.7 g distilled water. Analysis of the resulting two-phasehigh-acid aqueous composition revealed the following: Solids, 31.1%;Microaggregates, 0.07%; pH 2.1; Viscosity, 600 cps (#2 spindle, 60 rpm).

Example 10

A two-phase high-acid aqueous composition was prepared according to a"multi-staged continuous synthesis" process.

More specifically, a reactor vessel was equipped with a mechanicalstirrer, a reflux condenser, a thermometer, an N₂ inlet line, a monomerfeed line and a sampling tube/initiator injection line. 2747.72 gdistilled water was heated to 80° C. while deaerating. 75 g acrylic acidwas added to the reactor, stirred, then followed by an initiatorsolution prepared from 4.93 g ammonium persulfate in 30.0 g distilledwater. After stirring for approximately 25 minutes, a AA:BuA monomer mixwas gradually fed into reactor vessel over a period of 197.26 minutes.The AA:BuA monomer mix was prepared from 194.1 acrylic acid, 597.9 gbutyl acrylate, and 4.0 g divinyl benzene. At the conclusion of theAA:BuA monomer feed, an acrylic acid monomer mix was gradually fed intothe reactor vessel over a period of 56.0 minutes. The acrylic acidmonomer mix was prepared from 328.8 g acrylic acid and 5.0 gisopropanol. The solution was then held at 80° C. for 30 minutes, thencooled to 50° C. 3.32 g t-butyl peroxybenzoate was added and thesolution mixed for 5 minutes. The solution was held at 50° C. for 60minutes with a solution of 2.5 g sodium bisulfite in 12.5 g distilledwater added within the first 15 minutes. The final solution was cooledto 25° C. Analysis of the two-phase high-acid aqueous compositionrevealed the following: Solids, 29.98%; Microaggregates, 0.003% (on 45μm) and 0.0157% (on 5 μm); Viscosity, 1410 cps; Coagulum, none).

Example 11

A two-phase high-acid aqueous composition was prepared according to a"multi-staged continuous synthesis" process, having an extended acrylicacid monomer feed time.

A 5 l reaction flask was equipped with a stirrer (set at 200 rpm),condenser, thermometer, nitrogen sparge/sweep, and addition tubes formonomer addition. 2737.4 mls of distilled water were charged into theflask and heated to 80° C. Upon reaching 80° C., the nitrogen sparge wasswitched to sweep. 84.6 g acrylic acid was charged into the flask andmixed for 5 minutes. An initiator solution of 4.92 g ammonium persulfatein 30.0 mls distilled water was added into the reaction flask and thesolution mixed for 20 minutes. An AA:BuA monomer mix was then graduallyfed into the reaction flask over a period of 90 minutes (9.0 ml/min.).At the end of the feed, the solution was mixed for an additional 10minutes. 367.3 g acrylic acid was then gradually fed into the reactorover a period of over 180 minutes (approx. 1.95 ml/min.). The solutionwas held at 80° C. for 30 minutes, then cooled to 50° C. 3.32 g t-butylperoxybenzoate was added and mixed at 360 rpm for 5 minutes. A solutionof 2.5 g sodium bisulfite in 12.4 mls distilled water was added over 15minutes. The solution was held at 50° C. for a total of 60 minutes, thencooled to 25° C. Inspection of the resulting two-phase high-acid aqueouscomposition revealed few microaggregates, and notably, the absence of"skin" formation after handling. Analysis revealed the following:Microaggregates, 0.015% (5 μm); Viscosity, 740 cPs (#2 spindle, 60 rpm);Solids, 30.7%.

Example 12

A two-phase high-acid aqueous composition (40:60 AA:BuA) was preparedaccording to a "multi-staged continuous synthesis" process, having anextended acrylic acid monomer feed time. The process followed in essencethe process of Example 11. However, the AA:BuA monomer mix was made from180.8 g acrylic acid, 723.1 butyl acrylate, and 4.8 g divinyl benzene;and the acrylic acid monomer feed utilized 216.6 g acrylic acid. As withExample 12, inspection of the resulting two-phase high-acid aqueouscomposition revealed both few microaggregates and the absence of "skin"formation after handling.

Example 13

A two-phase high-acid aqueous composition (60:40 AA:BuA) was preparedaccording to a "multi-staged continuous synthesis" process, having anextended acrylic acid monomer feed time. The process followed in essencethe process of Example 11. However, the AA:BuA monomer mix was made from120.6 g acrylic acid, 482.0 butyl acrylate, and 3.2 g divinyl benzene;and the acrylic acid monomer feed utilized 517.9 g acrylic acid. As withExamples 11 and 12, inspection of the resulting two-phase high-acidaqueous composition revealed both few microaggregates and the absence of"skin" formation after handling.

Example 14

A two-phase high-acid aqueous composition was prepared according to an"in situ synthesis" process utilizing an acrylic acid/butyl acrylateseed.

More specifically, in a 1 l reaction flask equipped with a mechanicalstirrer (270-280 rpm), reflux condenser, nitrogen inlet line,thermometer, and feed lines, 1469.7 g distilled water was heated to 80°C. while deaerating. After the system was sparged with nitrogen asExample 7, 37.9 g acrylic acid and 4.8 g butyl acrylate were added andfollowed by the addition of an initiator solution made from 3.51 gpotassium persulate in 171.6 g distilled water (10 ml of the potassiumpersulfate was added an held for 10 minutes, and followed by theremaining solution fed at 24.3 ml/min. At the conclusion of the "insitu" seed polymerization, an AA:BuA monomer mix (328.4 g acrylic acid,361.4 g butyl acrylate, and 2.5 g divinyl benzene) was fed into thereactor over 242 minutes at a feed rate of 3.3 ml/min. The remainingsteps (post-catalyst steps) followed essentially as Example 7 utilizing1.99 g t-butylperoxybenzoate and a solution of 1.05 g NaH₂ SO₃ in 17.2 gdistilled water. Analysis of the resulting two-phase high-acid aqueouscomposition revealed the following: Solids, 31.00%; Microaggregates,0.193%; Viscosity, 2770 cps (#4 spindle, 60 rpm); Coagulum, <0.01%.

Tables 1A-1C: Acid Partitioning Data for Two-Phase Acidic AqueousCompositions

Acid partitioning data was collected for two-phase acidic aqueouscompositions of varying AA:BuA ratios and varying methods of synthesis.

Acid partitioning involved the separation of aqueous and particle phasesby ultracentrifuge. The composition of the aqueous phase polymer wassubsequently analyzed through NMR techniques. From the composition ofthe aqueous phase polymer and the partitioning of the total polymerbetween aqueous and particle phases, the partitioning of AA and BuAbetween the two phases was calculated as follows: ##EQU1## whereinAA_(aq).pol. is the weight fraction of acrylic acid in aqueous polymerof total polymer, AA_(total) is the weight fraction of acrylic acid intotal polymer, BuA_(latex) is the weight fraction of butyl acrylate inlatex of total polymer, γ_(aq).pol. is the weight fraction of aqueouspolymer in total polymer, X_(AA;aq).pol. is the weight fraction ofacrylic acid in aqueous polymer, X_(BuA;aq).pol. is the weight fractionof butyl acrylate in aqueous polymer, and X_(BuA;latex) is the weightfraction of butyl acrylate in latex, and BuA_(total) is the weightfraction of butyl acrylate in total polymer. Representative dam is setforth in Tables 1A-1C below.

                  TABLE 1A                                                        ______________________________________                                        Acid Partitioning Data for Two-Phase                                          Acidic Aqueous Compositions of 50:50 AA:BuA Ratios                            % Aqueous                                                                     Polymer of      Aqueous        Particle                                       Total   Sample  Phase Polymer  Phase Polymer                                  Polymer Temp.   % AA      % BuA  % AA   % BuA                                 ______________________________________                                        25.5    70° C.                                                                         91.5      8.46   35.8   64.2                                  24.8    70° C.                                                                         89.7      10.3   29.6   63.1                                  31.1    70° C.                                                                         91.3      8.67   31.8   68.2                                  30.9    70° C.                                                                         93.7      6.28   30.5   69.5                                  31.7    80° C.                                                                         87.5      12.5   32.6   67.4                                  35.5    80° C.                                                                         89.0      11.0   28.5   71.5                                  32.8    80° C.                                                                         89.0      11.0   31.0   69.0                                  32.9    80° C.                                                                         88.9      11.1   30.9   69.1                                  27.4    70° C.                                                                         94.0      5.96   33.4   66.6                                  27.9    70° C.                                                                         93.7      6.27   33.1   66.9                                  31.5    75° C.                                                                         88.5      11.5   32.3   67.7                                  31.0    75° C.                                                                         89.0      11.0   32.5   67.5                                  30.5    80° C.                                                                         89.8      10.2   32.5   67.5                                  28.3    80° C.                                                                         89.9      10.1   34.3   65.7                                  31.4    80° C.                                                                         91.4      8.56   31.1   68.9                                  33.45.sup.α                                                                     80° C.                                                                         96.77     3.23   26.49  73.51                                 33.55.sup.α                                                                     80° C.                                                                         97.54     2.46   26.00  74.00                                 36.19.sup.β                                                                      80° C.                                                                         97.06     2.94   23.31  76.69                                 36.83.sup.α                                                                     80° C.                                                                         96.58     3.42   22.84  77.16                                 32.87.sup.β                                                                      80° C.                                                                         98.89     3.11   26.07  72.96                                 ______________________________________                                         .sup.α Sample prepared by a Colloidally Stabilized StepWise             Synthesis.                                                                    .sup.β Sample prepared by an Extended Colloidally Stabilized StepWis     Synthesis.                                                               

                  TABLE 1B                                                        ______________________________________                                        Acid Partitioning Data for Two-Phase                                          Acidic Aqueous Compositions of 60:40 AA:BuA Ratios                            (Polymerization Temp. 70° C.)                                          % Aqueous                                                                     Polymer of                                                                            Aqueous                                                               Total   Phase Polymer   Particle Phase Polymer                                Polymer % AA     % BuA      % AA    % BuA                                     ______________________________________                                        41.8    85.3     14.7       41.8    58.2                                      45.7    91.7     8.28       33.3    66.7                                      41.6    90.8     9.23       38.1    61.9                                      41.8    91.3     8.73       37.5    62.5                                      42.2    91.1     8.88       37.3    62.7                                      40.5    91.5     8.54       38.6    61.4                                      48.14.sup.α                                                                     89.6     10.4       32.5    67.5                                      35.9    94.0     6.01       41.0    59.0                                      ______________________________________                                         .sup.α Polymerization Temperature: 80° C.                   

                  TABLE 1C                                                        ______________________________________                                        Acid Partitioning Data for Two-Phase                                          Acidic Aqueous Compositions of Varying AA:BuA Ratios                          Samples  % Aqueous                                                            AA:BUA   Polymer of                                                                              Aqueous      Particle                                      Ratio    Total     Phase Polymer                                                                              Phase Polymer                                 (Temp.)  Polymer   % AA    % BuA  % AA  % BuA                                 ______________________________________                                        20:80 (80° C.)                                                                  5.72      90.3    9.7    15.7  84.3                                  24:76 (80° C.)                                                                  8.35      91.5    8.5    17.6  82.4                                  24:76 (80° C.)                                                                  9.72      91.6    8.4    16.5  83.5                                  25:75 (80° C.)                                                                  10.4      92.4    7.56   17.0  83.0                                  30:70 (80° C.)                                                                  11.5      92.3    7.72   21.9  78.1                                  36:64 (80° C.)                                                                  16.2      93.6    6.40   25.3  74.7                                  40:60 (70° C.)                                                                  23.21     91.8    8.16   24.33 75.7                                  40:60 (70° C.)                                                                  21.27     91.7    8.33   26.04 74.0                                  ______________________________________                                    

                                      TABLE 2                                     __________________________________________________________________________    Curl Data Summary                                                             (@ 15% rel. hum.)                                                             Two-phase acidic aqueous compositions of varying AA:BuA                       ratios were incorporated into diffusion transfer products, the diffusion      transfer                                                                      products having either an aqueous-based or solvent-based barrier. Curl        data                                                                          was collected for each sample and are summarized in the table, below.         Control                                                                       compositions having neutralization layer compositions comprising solvent      based                                                                         polymers are provided for reference.                                          __________________________________________________________________________    Composition                                                                           Method of Synthesis                                                                       Meq.                                                                              Barrier  Curl (.sup.β)                           __________________________________________________________________________    Control 1                                                                             Blend of Solvent                                                                          16.5                                                                              None     44 ± 5                                            Based Polymers                                                        Control 2                                                                             Blend of Solvent                                                                          16.5                                                                              Aqueous-based                                                                          47 ± 4                                            Based Polymers                                                        AA:BuA  Method of Synthesis                                                                       Meq.                                                                              Barrier  Curl (.sup.β)                           Composition                                                                           (.sup.α)                                                        40:60   Simultaneous                                                                              18.2                                                                              None     34-36                                                synthesis                                                             50:50   Simultaneous                                                                              18.2                                                                              Solvent-based                                                                          43 ± 3                                            synthesis                                                             50:50.sup.γ                                                                     Colloidally stabilized;                                                                   18.2                                                                              Aqueous-based                                                                          38 ± 5                                            Blend.                                                                50:50   Colloidally stabilized                                                                    18.0                                                                              Solvent-based                                                                          45                                                   ("in situ");                                                                  simultaneous synthesis                                                50:50   Colloidally stabilized                                                                    18.2                                                                              Aqueous-based                                                                          50 ± 3                                            ("in situ");                                                                  simultaneous synthesis                                                50:50   Colloidally stabilized                                                                    13.7                                                                              Solvent-based                                                                          42 ± 4                                            ("in situ");                                                                  simultaneous synthesis                                                50:50   Colloidally stabilized                                                                    13.7                                                                              Solvent-based                                                                          38 ± 2                                            ("in situ");                                                                  simultaneous synthesis;                                                       no cross-linker                                                       50:50   Colloidally stabilized                                                                    18.2                                                                              Aqueous-based                                                                          47 ± 5                                            step-wise synthesis                                                   AA:BuA  Method of Synthesis                                                   Composition                                                                           (.sup.α)                                                                            Meq.                                                                              Barrier  Curl (β)                                __________________________________________________________________________    50:50   Colloidally stabilized                                                                    16.4                                                                              Solvent-based                                                                          45                                                   step-wise synthesis                                                   50:50   Colloidally stabilized                                                                    13.7                                                                              Solvent-based                                                                          38                                                   step-wise synthesis                                                           (extended)                                                            50:50   Colloidally stabilized                                                                    18.2                                                                              Solvent-based                                                                          41                                                   step-wise synthesis                                                           (extended)                                                            50:50   Colloidally stabilized                                                                    21.7                                                                              Solvent-based                                                                          39                                                   step-wise synthesis                                                           (extended)                                                            50:50   Colloidally stabilized                                                                    21.7                                                                              Aqueous-based                                                                          48                                                   step-wise synthesis                                                           (extended)                                                            60:40   Simultaneous                                                                              18.2                                                                              Aqueous-based                                                                          49 ± 4.sup.-                                      synthesis                                                             60:40   Colloidally stabilized                                                                    18.2                                                                              Aqueous-based                                                                          53                                                   step-wise synthesis                                                   __________________________________________________________________________     .sup.α Labels for the methods provided herein refer to methods that     are more fully described above and should accordingly be referentially        construed.                                                                    .sup.β Curl = 10.sup.3 × 1/r, where r is the radius of the         curvature. Standard deviation values are provided where at least 4            repeated measurements were available.                                         .sup.γ Includes blends utilizing 28:80 AA:BuA and 30:70 AA:BuA          particles, with various amounts of Poly(acrylic acid) colloidal               stabilizer.                                                              

                  TABLE 3                                                         ______________________________________                                        Post Process pH Measurements                                                  (6 day 49° C./55% rel. hum. incubation)                                        Method of                                                                     Synthesis                 Post-Process                                Sample  (.sup.α)                                                                              Barrier Layer                                                                             pH                                          ______________________________________                                        Control A                                                                             Blend of Solvent                                                                            None        7.33                                                Based Polymers                                                        Control B                                                                             Blend of Solvent                                                                            None        7.15                                                Based Polymers                                                        Control C                                                                             Blend of Solvent                                                                            Aqueous Based                                                                             7.24                                                Based Polymers                                                        Sample 1                                                                              Colloidally                                                                   Stabilized ("in                                                                             Aqueous Based                                                                             6.98                                                situ");                                                                       Simult. Synthesis                                                     Sample 2                                                                              Colloidally   Aqueous Based                                                                             6.89                                                Stabilized ("in                                                               situ");                                                                       Simult. Synthesis                                                     Sample 3                                                                              Colloidally   "           7.18                                                Stabilized ("in                                                               situ");                                                                       Simult. Synthesis                                                     Sample 4                                                                              Colloidally   "           6.71                                                Stabilized ("in                                                               situ");                                                                       Simult. Synthesis                                                     Sample 5                                                                              Colloidally   "           7.07                                                Stabilized ("in                                                               situ")                                                                        Simult. Synthesis                                                     Sample 6                                                                              Colloidally   "           7.06                                                Stabilized ("in                                                               situ");                                                                       Simult. Synthesis                                                     Sample 7                                                                              Colloidally   "           7.16                                                Stabilized ("in                                                               situ");                                                                       Simult. Synthesis                                                     Sample 8                                                                              Colloidally   "           7.24                                                Stabilized ("in                                                               situ");                                                                       Simult. Synthesis                                                     Sample 9                                                                              Colloidally   "           6.98                                                Stabilized ("in                                                               situ");                                                                       Simult. Synthesis                                                     Sample 10                                                                             Colloidally   "           7.00                                                Stabilized ("in                                                               situ");                                                                       Simult. Synthesis                                                     Sample 11                                                                             Colloidally   "           6.88                                                Stabilized ("in                                                               situ");                                                                       Simult. Synthesis                                                     Sample 12                                                                             Colloidally   "           6.95                                                Stabilized; Blend                                                     Sample 13                                                                             Colloidally   "           6.88                                                Stabilized; Step-wise                                                         Synthesis                                                             ______________________________________                                         .sup.α Labels for the methods provided herein refer to methods that     are more fully described above and should accordingly be referentially        construed.                                                               

We claim:
 1. A method for preparing a two-phase acidic aqueouscomposition comprising a discontinuous acidic particle phase and acontinuous aqueous phase, the method comprising the steps of:providingan aqueous solution of a colloidal stabilizer in a reactor vessel, thecolloidal stabilizer comprising a linear polymeric acid, the linearpolymeric acid comprising recurring monomeric units of an ethylenicallyunsaturated organic acid monomer; adding a mixture of copolymerizablemonomers to the aqueous colloidal stabilizer solution in the reactorvessel, the mixture of copolymerizable monomers comprising anethylenically unsaturated organic acid monomer and an ethylenicallyunsaturated organic ester monomer, the ethylenically unsaturated organicacid monomer capable of forming salts with alkali metals or with organicbases, the ethylenically unsaturated organic ester monomer capable ofpromoting insolubility of the particle phase in the aqueous phase;copolymerizing the copolymerizable monomers in the aqueous colloidalstabilizer solution to form a discrete acidic particle; and introducingan acidic aqueous polymer into the aqueous solution to surroundinglysupport the discrete acidic particle and thereby form the two-phaseacidic aqueous composition, the acidic aqueous polymer phase comprisingan aqueous acid polymer having recurring monomer units of at least anorganic acid monomer, the aqueous acid polymer capable of interactingwith the acidic particle phase at an interface such that the acidicparticle phase polymer is brought into intimate association with thecontinuous aqueous phase.
 2. The method of claim 1, wherein the acidicaqueous polymer is provided by blending the acidic particles with apresynthesized linear polymeric acid.
 3. The method of claim 2,whereinthe aqueous phase polymer is a presynthesized linear, partiallyneutralized polymeric acid; and the average molecular weight of thelinear polymeric acid of the colloidal stabilizer is less than theaverage molecular weight of the linear polymeric acid of the aqueousphase polymer.
 4. The method of claim 1, wherein the colloidalstabilizer is provided in the reactor vessel by in situ polymerizationof the colloidal stabilizer monomeric units.
 5. The method of claim 4,wherein the aqueous acid polymer further comprises recurring monomericunits of an organic ester monomer.
 6. The method of claim 5, wherein theacidic aqueous polymer phase is provided by copolymerizing the monomericunits of the aqueous acidic polymer simultaneously with the acidicparticle copolymerization step.
 7. The method of claim 1, wherein theacidic aqueous phase is provided in a subsequent step by polymerizingthe monomeric units of the aqueous acidic polymer immediately followingthe particle phase copolymerization in the same reactor vessel.